Dyeing process



Patented Nov. 8, 1938 UNITED STATES 2,135,633 PATENT OFFICE.

DYEING PROCESS I 'Berthold Bienert, Ieverkusen-I. G. Work, and

Karl Holzach,

Lndwigshafen on-the-khine,

Germany, asslgnors to General Aniline Works, Inc., New York, N. Y., acorporation of Dela- No Drawing. Application May 2, 1936, Serial No.77,628. In-Germany May 9, 1935 7 Claims.

0 copper, nickel, cobalt, iron or zinc in a nonionizable complex linkwhereasothers are free from metals. Both metal-free and metal-containingcompounds are "included by the term phthalocyanines". It is known thatthese phthalocyanines can be sulfonated by the action of fuming sulfuricacid, the number of the sulfuric acid groups entering the moleculedepending on the temperature and the strength of the fuming sulfuricacid. Our present invention is limited to the use of the sulfonic acidsof such phthalocyanines as are substantially identical with thoseobtainable by heating ortho-arylenedinitriles of the benzene ornaphthalene series with metals, metal compounds and ammonia or ammoniumsalts. For convenience, compounds of this type are called in thefollowing phthalocyanines of the benzene and naphthalene series.

We have now discovered that sulfonic acids of phthalocyanines of thecharacter described are capable of directly dyeing cellulosic materials.Brilliant shades of excellent fastness to light are obtained. This isthe more surprising as most of the sulfonic acids of other dyestuffsshow afllnity towards vegetable fibers only in case diphenyl groups orsimilar groups are present. term "cellulosic materials we mean vegetablefibers, such as cotton, cuprammonium or viscose silk, furthermore, paperor raw materials for the preparation thereof, such as paper pulp,pasteboard, straw, cellulose, jute, linters, cotton, wool, sponges andso on. For the dyeing of textiles such compounds are preferred, ascontain about 1 to 2 sulfonic acid groups in the molecule, whereas incase of paper or raw materials for the preparation thereof highersulfonated compounds, which contain about 3 sulfonic acid groups in themolecule are preferably employed. The dyeing of such asoleyl-oxy-ethane-sulfonic acid can be added to the dyeing bath.

The sulfonic acids of the copper-containing dyestufis yield sky-blueshades, while the sulfonic acids of the nickel or zinc containingdyestufis and those of the metal free dyestuflfs yield more greenishshades. The dyeings, which are By the (Cl. 8a-1) obtained from thesulfonic acids of the cobaltcontaining dyestuffs, are'of a morereddish-blue tint, while the iron-containing dyestuffs yield steel-bluedyeings.

The fastness to water of the dyeings on textiles may be still furtherimproved by subjecting the same to an aftertreatment with organicbasicreacting compounds, which are capable of forming diilicultlysoluble salts with'the sulfonic acids and show affinity towardscellulosic materials, As example for these basic-reacting compoundsthere may be mentioned ethylene diamine, which is partially acylated bymeans of a higher fatty acid, polyethylene polyamines, which are eitherperalkylated or likewise partially acylated by means of a higher fattyacid, furthermore ammonium, phosphonium or sulfonium bases with higheralkyl groups such as cetylpyridinium bromide orbenzylethyl-dodecylsulfonium chloride.

The following examples illustrate the invention, without, however,restricting it thereto, the parts being by weight.

EXAMPLE 1 g Dyeing of cotton with metal-containing dyestufis 1 part of asulfonic acid of a metal-containing phthalocyanine is dissolved in 100parts of water; 1 part of soda dissolved in 10 parts of water and 10parts of sodium sulfate dissolved in 100 parts of water are addedthereto. The solution is then made up with hot water to 1000 parts. Inthe dyeing bath thus obtained 50 parts of cotton are dyed for 1 hour atBil- C. Thereupon it is rinsed and dried. Clear shades of excellentfastness to light are thus obtained which in case of applyingacopper-containing phthalocyanine sulfonic acid show a sky-blue shade,in case of applying a nickel-containing phthalocyanine sulfonic acidshow a more greenish shade and in case of applying a cobalt-containingdyestufi show a more reddish tint. Clear green shades are obtained byapplying a dyestufi obtained in the following manner:

'10 parts of the copper-phthalocyanine, which is obtainable from1.2-dicyanonaphthalene by heating with copper salt, are introduced intoparts of a 30% fuming sulfuric acid and stirred for 1 hour at roomtemperature. The reaction mixture is poured onto ice and theprecipitating sulfonic acid filtered off by suction. The sulfonic acidis then neutralized by means of soda and isolated by salting out.

EXAMPLE 2 Dyeing of cotton with metal-free dyetufis A metal-freephthalocyanine, which is obtained by heating a phthalonitrile in thepresence of sodium amylate, is sulfonated by a treatment with a 32%fuming sulfuric acid at 70-80 c,

1 part; of 'the'-sodium salt, of-the sulfonic acid thus' obtainedis-dissolved in 100 parts of water. After the addition of 1 part of sodaand 10 parts of sodium sulfate the mixture is filled up with 'water to1,000 parts. In this dyeing liquor 50 bluish-green shares of goodfastness to water and Y washing are obtained.

EXAMPLE 3 Dyeing of viscose-artificial silk 0.8 part of sulfonic acid ofa phthalocyanineare dissolved in 100 parts of water. 20 parts of sodiumsulfate dissolved in 200 parts of water are then added and the solutionis made up with hot water to 1,000 parts. Into the dyeing bath thusobtained 40 parts of viscose silk are dyed for one hour at 85-90 C.After dyeing the viscose silk is rinsed and dried.

For this dyeing process metal-containing as well as metal-freephthalocyanines may be employed. Clear bluish-green shades are obtainedby using the sulfonic acid of a zinc phthalocyanine, which may beprepared in the following manner:

30 parts of zinc phthalocyanine which is obtained by heatingphthalonitrile with zinc oxide and formamide are heated for 2 hours with300 parts of a fuming sulfuric acid of a sulfur trioxide content of 30%.The sulfonic acid is isolated by pouring the reaction solution obtainedonto ice. It is converted into its sodium salt by mixing with water,neutralizing with soda and salting out in the usual manner.

EXAMPLE 4 Dyeing of sulfite cellulose pulp Bleached sulfite cellulosepulp is dyed in the usual manner in the'hollander with 1% of the sodiumsalt of a copper-phthalocyanine sulfonic acid, which is obtained bysulfonating the copperphthalocyanine with a 30% fuming sulfuric acid,and, if necessary, sized with a 3% resin soap and 4% aluminum sulfate.The paper pulp thus obtained is worked up in the usual manner to paper.An evenly dyed paper is thus obtained which is distinguished by anespecially brilliant blue shade.

Instead of the sulfite cellulose pulp there may be used with the sameresult a paper pulp consisting of 50% of mechanical wood pulp and.

-in the usual manner and converted into the sodium salt. This sulfonicacid yields greenish shades.

EXAMPLE 5 Dyeing of paper 30 parts of a copper phthalocyanine sulfonicacid are dissolved in 1,000 parts of water. The solutionis kept at atemperature (for example 40 C.) sufiicient to keep it in solution. Thinpaper may be dyed by'a simple dipping into or passage through thissolution. Brilliant blue shades are thus obtained. Also in this case thesulfonic acid of the metal-free phthalocyanines or of metal-containingphthalocyanines may be employed. I

Exmru 6 Dyeing of a film of regenerated cellulose A. colorless film of.regenerated cellulose is passed for 2 minutes through an aqueous dyebath consisting of 1% of the sodium salt of the sulfonic acid of ametal-free phthalocyanine and 5% of glycerine. The film is subsequentlydried in a suitable drying apparatus. A clear greenish blue shade isthus obtained.

Other phthalocyanine sulfonic acids, such as the copper-containingdyestuif, may be employed with a similar result.

We claim:

1. The process of dyeing cellulosic materials which comprises directlyapplying to such materials unreduced sulfonic acids of phthalocyaninesselected from the group consisting of phthalocyanines of the benzene andnaphthalene series.

2. The process of dyeing cellulosic materials which comprises directlyapplying to such materials unreduced sulfonic acidsv of phthalocyaninesselected from the group consisting of phthalocyanines of the benzeneandnaphthalene series containing copper in complex combination.

3. The process of dyeing cellulosic materials which comprises directlyapplying to such materials unreducd sulfonic acids of metal-freephthalocyanines selected from the group consisting of phthalocyanines ofthe benzene and naphthalene series.

4. The process of dyeing textiles from cellulosic materials whichcomprises directly applying to such materials unreduced sulfonic acidsof phthalocyanines selected from the group consisting of phthalocyaninesof the benzene and naphthalene series containing one to two sulfonicacid groups in the molecule.

5. The process of dyeing paper which comprises directly applying to thepaper unreduced sulfonic acids of phthalocyanines selected from thegroup consisting of phthalocyanines of the benzene and naphthaleneseries containing three sulfonic acid groups in the molecule.

6. The process of dyeing textiles from cellulosic materials whichcomprises directly applying to such materials unreduced sulfonic acidsof phthalocyanines selected from the group consisting of phthalocyaninesof the benzene and naphthalene series and subjecting the dyeings thusobtained to an after-treatment with organic basicreacting compoundswhich are capable of forming insoluble salts with the phthalocyaninesulfonic acids.

'7. The process of dyeing cellulosic materials which comprises directlyapplying to such materials unreduced sulfonic acids of phthalocyaninesselected from the group consisting of phthalocyanines of the benzene andnaphthalene series containing nickel in complex combination BERTHOLDBIENERT. KARL HOLZACH.

